CN101796125B - Elastomer thermoplastic mixtures and compositions having improved properties, method of making said compositions and applications thereof - Google Patents

Elastomer thermoplastic mixtures and compositions having improved properties, method of making said compositions and applications thereof Download PDF

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CN101796125B
CN101796125B CN200880104983.6A CN200880104983A CN101796125B CN 101796125 B CN101796125 B CN 101796125B CN 200880104983 A CN200880104983 A CN 200880104983A CN 101796125 B CN101796125 B CN 101796125B
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mixture
composition
grafting
crosslinked
polyamide
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CN101796125A (en
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M·赫特
D·朱塞特
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Arkema SA
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Arkema SA
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    • C08L51/00—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers
    • C08L51/06—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers grafted on to homopolymers or copolymers of aliphatic hydrocarbons containing only one carbon-to-carbon double bond
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    • C08F255/02—Macromolecular compounds obtained by polymerising monomers on to polymers of hydrocarbons as defined in group C08F10/00 on to polymers of olefins having two or three carbon atoms
    • C08F255/026—Macromolecular compounds obtained by polymerising monomers on to polymers of hydrocarbons as defined in group C08F10/00 on to polymers of olefins having two or three carbon atoms on to ethylene-vinylester copolymers
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    • C08L23/18—Homopolymers or copolymers of hydrocarbons having four or more carbon atoms
    • C08L23/20—Homopolymers or copolymers of hydrocarbons having four or more carbon atoms having four to nine carbon atoms
    • C08L23/22—Copolymers of isobutene; Butyl rubber ; Homo- or copolymers of other iso-olefins
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    • C09D151/00—Coating compositions based on graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Coating compositions based on derivatives of such polymers
    • C09D151/06—Coating compositions based on graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Coating compositions based on derivatives of such polymers grafted on to homopolymers or copolymers of aliphatic hydrocarbons containing only one carbon-to-carbon double bond
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    • C09J151/00—Adhesives based on graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Adhesives based on derivatives of such polymers
    • C09J151/06—Adhesives based on graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Adhesives based on derivatives of such polymers grafted on to homopolymers or copolymers of aliphatic hydrocarbons containing only one carbon-to-carbon double bond
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    • C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
    • C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
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    • C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
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    • C08L23/36—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers modified by chemical after-treatment by reaction with compounds containing nitrogen, e.g. by nitration
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    • C08L2666/00—Composition of polymers characterized by a further compound in the blend, being organic macromolecular compounds, natural resins, waxes or and bituminous materials, non-macromolecular organic substances, inorganic substances or characterized by their function in the composition
    • C08L2666/02—Organic macromolecular compounds, natural resins, waxes or and bituminous materials

Abstract

The mixture of the invention contains, for 100 parts in weight of (A) + (B): (A) 10 to 90 parts in weight of at least one non-nanostructured olefinic thermoplastic polymer; (B) 90 to 10 parts in weight of a formulation of at least one elastomer having unsaturated double bonds and capable of reacting with a cross-linking or vulcanisation agent, said formulation containing a cross-linking or vulcanisation system of said elastomer(s), at least one plasticizer and the standard additives present in elastomer formulations; (C) up to 100 parts in weight relative to (A) + (B) of at least one copolymer grafted with polyamide blocks, said copolymer comprising a polyolefine trunk and at least 1.3 polyamide grafts on said trunk in average and having a nano-structured organisation, wherein said grafts are attached to the trunk by the rest of an unsaturated monomer (X) having a function capable of reacting with a polyamide with an amine end, the rest of said unsaturated monomer (X) being attached on the trunk by grafting or copolymerisation from the double bond thereof, and wherein (A) and (B) in the mixture can already have been combined together by the cross-linking or vulcanisation dynamic method in order to provide a cross-linked or vulcanised thermoplastic composition.

Description

There is method of the elastomer thermoplastic mixtures of improved character and composition, the described composition of manufacture and uses thereof
The present invention relates to thermoplastic olefin polymer with the mixture of crosslinked or vulcanization system and the unsaturated elastic body that is mixed with by softening agent, filler and other typical additives traditionally.
The invention still further relates to by the dynamic vulcanization of this class preparation elastomerics in this class olefinic thermoplastic polymer or the method for the corresponding composition for thermoplastic elastomer of crosslinked preparation.
Its relate to acquisition like this composition for thermoplastic elastomer, they for especially by extruding, injection molding and compression moulding technology manufacture the purposes of end article and thus obtained the finished product.
The foremost thermoplastic elastomer with rubber properties is the product by elastomerics-obtain as the dynamic vulcanization process of ethylene-propylene-diene (EPDM) elastomerics of preparation-in the polypropylene (PP) of common polyolefin-type matrix-particularly or polyethylene (PE).
In this method, thermoplastics (as PP or PE) is mixed with the elastomerics being mixed with vulcanization system (as EPDM), this elastomerics is crosslinked in mixing process.
Products obtained therefrom is known as " thermoplastic vulcanizate " (TPV) and consists of the thermoplastic matrix that is coated the rubber particles of several microns big or small, and rubber phase can be main phase (maximum 85 % by weight).These products can be as thermoplastics by extruding or injection molding is used, there is the character of rubber phase, i.e. low compression or tensile-permanent set simultaneously.
But these alloys have thermodynamical restriction intrinsic in the thermoplastic polymer in the matrix of being used in, and for for PP matrix and the elastomeric thermoplastic vulcanizate of EPDM (TPV), the use temperature that PP causes is limited to 130 ℃.In addition, the modulus in flexure of PP and high rigidity cause the alloy with suitable high rigidity.
International pct application WO 02/28959A1 has described has the flexible polyolefinic mixture that the graft copolymer of polyamide-block and they and flexural modulus of elasticity are less than 150MPa.The flexible mixture of these low modulus does not have caoutchouc elasticity under 70 ℃ or higher temperature, because the polyolefine in this mixture is hemicrystalline, fusing point is 60 ℃ to 100 ℃.
Have been found that these multipolymers with polyamide-block are organized into structure with nano level, this gives their outstanding thermodynamics intensive properties.This thermomechanical property shows as in 100 ℃ to 180 ℃ temperature ranges almost constant Young's modulus.
Especially by monoamine polymeric amide, being grafted to the graft polyolefin with polyamide-block that the technology on the maleic anhydride of ethylene/butyl acrylate/maleic anhydride type terpolymer obtains is the flexible thermoplastic plastics with high thermodynamics intensity.They show relatively high flexural modulus of elasticity, especially lower than 200MPa with higher than 50MPa, and the dynamic elastic modulus of the 0.5MPa to 10MPa recording at 150 ℃.This modulus, in the wide temperature range of 80 to 180 ℃, or is relative constant in example between the fusing point (80-100 ℃) of ethylene/butyl acrylate/maleic anhydride terpolymer and the fusing point (180-220 ℃) of polymeric amide.
But these multipolymers with polyamide-block are not elastomericss, because their low compressed residual elasticity when surpassing 80 ℃.Can say, they do not have the caoutchouc elasticity that the per-cent with compression set (DRC) represents.Thermoplastic elastomer has and is usually less than 50%, or 30% DRC even, and the graft polyolefin with polyamide-block has common 60% to 80% DRC.
Patent US 4,130, and 535 have described the alloy with softening agent preparation completely crosslinked olefinic rubber of thermoplastic elastomer based on 25% to 75% and 75% to 25%.This thermoplastic polymer is polypropylene.
Patent EP 384 822 has described multipolymer based on ethene and alpha-olefin and the composition of rubber, this rubber is based on plasticising and crosslinked polynorbornene, its plasticization capacity due to polynorbornene and select thermoplastic polymer to have from fusing point is no more than the ethylene copolymer of 130 ℃ to be no more than 65 Xiao A hardness.These alloys have 45% the compression set of being less than recording at 70 ℃.
European patent application EP 1672027 has been described the thermoplastic polymer composition obtaining by mixed rubber (wherein 30 % by weight or higher gel section are dispersed in based in polymeric amide and/or the polymkeric substance based on polyester) and the dynamic crosslinking by this rubber.This analog thermoplastic polymkeric substance based on polymeric amide or polyester has the shortcoming that does not show good resistance to hydrolysis and salt resistance and do not show low Xiao A hardness.
United States Patent (USP) 5,843,577 have described the thermoplastic elastomer with improved surface properties, and it is by mixing the multipolymer of functionalised polyolefin and polymeric amide in described thermoplastic elastomer and obtain.
The object of this invention is to provide and compare the TPV type alloy that there is augmented performance but do not sacrifice the premium properties of this class system with known architectures.Therefore, with respect to based on polyacrylic known architectures, consider that polypropylene is in about 130-140 ℃ of its performance of loss, object particularly improved temperature performance, obtain the possibility of soft more and be adhered to the possibility on other material, especially polymeric amide.With respect to the known architectures based on polymeric amide, object is better resistance to hydrolysis and anti-salt (as zinc chloride) property and obtain the more possibility of soft particularly.
The flexible thermoplastic base-material with high heat resistance used according to the invention is realized these objects, described base-material all keeps its performance and forms still comprising free functional group to about 170-180 ℃, as the external phase of free maleic anhydride group, bonding with as the material of polymeric amide or metal and so on of the TPV that promotes thus gained.TPV of the present invention can be used for being manufactured on-40 ℃ to the goods in the wide temperature range of 160 ℃ with favorable elasticity.
The present invention so first object are a kind of mixture, its every 100 weight parts (A)+(B) comprise:
(A) the structurized olefinic thermoplastic polymer of at least one non-nano of 10 to 90 weight parts;
(B) elastomeric preparation that at least one of 90 to 10 weight parts has unsaturated double-bond and can react with crosslinked or vulcanizing agent, described preparation comprises for being cross-linked or vulcanizing described elastomeric system, at least one softening agent and at the conventional additive of elastomer formulation.
(C) with respect to (A)+(B), at least one of maximum 100 weight parts has the graft copolymer of polyamide-block, described multipolymer is formed and is had nano-structured tissue by polyolefin backbone and on average at least 1.3 the polymeric amide grafting on described skeleton, and wherein said grafting can be connected on skeleton with the residue with the unsaturated monomer (X) of the functional group of aminoterminal polyamide reaction by having; And the described residue of described unsaturated monomer (X) is fixed to skeleton by grafting or copolymerization from its pair of key,
(A) in this mixture and (B) can be combine to produce sulfuration or crosslinked thermoplastic compounds by dynamic vulcanization or crosslinking.
The ratio of composition (A) is especially 15 to 75 weight parts, and composition (B) is correspondingly 85 to 25 weight parts.
With respect to (A)+(B), the ratio of composition (C) is especially 10 to 90 weight parts.
More particularly, composition (C) can form maximum 50 % by weight of mixture (A)+(C).
composition (A)
The polyolefine of composition (A) refers to alpha-olefin or diolefine, for example homopolymer or the multipolymer of ethene, propylene, but-1-ene, iso-butylene, penta-1-alkene, own-1-alkene, pungent-1-alkene, 3-Methyl-1-pentene, 4-methyl-1-pentene, 5-methyl isophthalic acid-hexene, divinyl.Example comprises:
The homopolymer of-ethene and multipolymer, particularly Low Density Polyethylene (LPDE), high density polyethylene(HDPE) (HPDE), LLDPE (LLPDE), very low density polyethylene (VLDPE) and the polyethylene obtaining by metallocene catalyst described in aforementioned PCT international application; Ethene and at least one alpha-olefin, for example C 3-C 8the multipolymer of alpha-olefin, as ethylene/propene copolymer, ethylene-propylene elastomeric (EPR) and ethylene/propylene/diene elastomerics (EPDM); Ethene and at least one are selected from the salt of unsaturated carboxylic acid or ester (as (methyl) vinylformic acid and C 1-C 8the ester of alcohol, for example methyl acrylate) or the multipolymer of the product of the vinyl acetate (as vinyl-acetic ester) of saturated carboxylic acid, the ratio of comonomer can reach 40 % by weight;
The homopolymer of-propylene and multipolymer;
-styrene/ethylene-butylene/styrene (SEBS), styrene/butadiene/styrene (SBS), styrene/isoprene/styrene (SIS) and styrene/ethylene-propylene/styrene (SEPS) segmented copolymer;
-olefin polymer, as with reactive monomer, more especially but use without limitation maleic anhydride copolymerization or functionalized ethene and the polymkeric substance of propylene.
composition (B)
Composition (B) consists of crosslinkable elastomeric and the several additive of 100 weight parts, and the amount of described additive represents with every 100 parts of elastomeric umbers (pcr).These additives in rubber industry in known mixing machine (as Banbury mixer and mill (m é langeur à cylindre)) enough low so that can not make to mix in elastomerics at elastomer crosslinked temperature (being usually less than 100 ℃).
Unsaturated elastic body is especially selected from:
The terpolymer of-ethene, propylene and diene (EPDM);
-based on (NR) divinyl, natural or synthetic elastomerics, and styrene-butadiene copolymer (SBR);
The multipolymer of-divinyl and vinyl cyanide (NBR);
The partial hydrogenation multipolymer (HNBR) of-divinyl and vinyl cyanide;
-elastomerics based on isoprene (IR);
-acrylic elastomer, as there is the acrylate copolymer of reactive acid or epoxy moieties, as the multipolymer (ACR) of methyl acrylate or butyl acrylate and acrylic or methacrylic acid glycidyl ester.
This is cross-linked or vulcanization system is suitable for elastomeric type used.Especially, for diene elastomer, it is selected from the vulcanizing agent of the compound based on sulphur, superoxide, resol, azo-based, maleimide amino, quinonoid compound and urethanum; For having the acrylic elastomer of acidic group, it is selected from based on polyfunctional amine, as hexyl diamino carbamate, or the reagent based on vulcabond; Or for having the acrylic elastomer of epoxide group, it is selected from based on ammonium salt, as the reagent of glyoxal ethyline or polyfunctional acid's molecule.
This ratio crosslinked or vulcanization system is well known by persons skilled in the art for obtaining the common ratio that is almost completely cross-linked or vulcanizes of elastomerics phase.
This crosslinked or vulcanization system more particularly constituent (B) 1 to 20pcr.
The common constituents of described one or more softening agent (B) 5 to 200pcr, and especially, for thering is the elastomerics of unsaturated double-bond, select the oil of the mixture formation of free aliphatic series, cycloalkanes or aromatic hydrocarbon, for acrylic elastomer, be selected from the polar oil based on phthalic ester.
Typical additives is generally selected from powdery mineral filler, and as zinc oxide, titanium oxide, carbon black, kaolin and silicon-dioxide, pigment, coupling agent, anti degradant, processing additives are as stearate, and wax, and especially constituent (B) 10 to 150pcr.
composition (C)
The graft copolymer that composition (C) has polyamide-block by least one described in international pct application WO 02/28959 forms, and can react and obtain with the residue that is fixed to the unsaturated monomer X on polyolefin backbone by grafting or copolymerization by making to have aminoterminal polymeric amide.This quasi-graft copolymer is to have the flexible thermoplastic plastics that high heating power is learned intensity.
Monomer X can be, for example, and unsaturated epoxide or unsaturated carboxylic acid anhydrides.
The example of unsaturated epoxide is, for example:
-aliphatic glycidyl ester and ether, as glycidyl allyl ether, vinyl glycidyl ether, toxilic acid glycidyl ester and glycidyl itoconate, glycidyl acrylate and glycidyl methacrylate; With
-alicyclic glycidyl ester and ether, as 2-tetrahydrobenzene 1-glycidyl ether, carboxylic acid tetrahydrobenzene-4,5-2-glycidyl ester, carboxylic acid tetrahydrobenzene-4-glycidyl ester, carboxylic acid 5-norbornylene-2-methyl-2-glycidyl ester, with cis-dicyclo in dicarboxylic acid [2.2.1]-5-heptene-2,3-2-glycidyl ester.
The example of unsaturated carboxylic acid anhydrides is maleic anhydride, itaconic anhydride, citraconic anhydride, allyl group succinyl oxide, hexamethylene-4-alkene-1 especially, 2-dicarboxylic anhydride, 4-methylene radical hexamethylene-4-alkene-1,2-dicarboxylic anhydride, dicyclo [2.2.1] heptan-5-alkene-2,3-dicarboxylic anhydride and methyl bicycle [2.2.1] heptan-5-alkene-2,2-dicarboxylic anhydride.It is favourable using maleic anhydride.Partly or entirely acid anhydrides can not deviated from scope of the present invention as (methyl) vinylformic acid substitutes by unsaturated carboxylic acid.
About polyolefin backbone, polyolefine refers to alpha-olefin or diolefine, for example homopolymer or the multipolymer of ethene, propylene, but-1-ene, pungent-1-alkene or divinyl.As an example, can mention:
The homopolymer of-ethene and multipolymer, particularly Low Density Polyethylene (LPDE), high density polyethylene(HDPE) (HPDE), LLDPE (LLPDE), very low density polyethylene (VLDPE) and the polyethylene obtaining by metallocene catalyst described in aforementioned international pct application; Ethene and at least one alpha-olefin, for example C 3-C 8the multipolymer of alpha-olefin, as ethylene/propene copolymer, ethylene-propylene elastomeric (EPR) and ethylene/propylene/diene elastomerics (EPDM); Ethene and at least one are selected from the salt of unsaturated carboxylic acid or ester (as (methyl) vinylformic acid and C 1-C 8the ester of alcohol, for example methyl acrylate) or the multipolymer of the product of the vinyl acetate (as vinyl-acetic ester) of saturated carboxylic acid, the ratio of comonomer can reach 40 % by weight;
The homopolymer of-propylene and multipolymer;
-styrene/ethylene-butylene/styrene (SEBS), styrene/butadiene/styrene (SBS), styrene/isoprene/styrene (SIS), styrene/ethylene-propylene/styrene (SEPS) segmented copolymer.
The polyolefine of the skeleton of the graftomer of composition (C) therefore can be selected from Alathon, alfon, ethene and C 3-C 8alpha-olefin, with (methyl) vinylformic acid and C 1-C 8the ester of alcohol and with the multipolymer of vinyl-acetic ester.
Advantageously, the residue of X connection polyolefin backbone is thereon with the polyethylene of X grafting or the multipolymer of the ethene for example obtaining by radical polymerization and X.
About X, be grafted to the polyethylene on it, polyethylene is understood to mean homopolymer or multipolymer.
As the comonomer that participates in these multipolymers structures, can mention:
-alpha-olefin, advantageously for thering are those of 3 to 30 carbon atoms, the example of this class alpha-olefin is propylene, 1-butylene, 1-amylene, 3-methyl-1-butene, 1-hexene, 4-methyl-1-pentene, 3-Methyl-1-pentene, 1-octene, 1-decene, 1-laurylene, 1-tetradecylene, 1-hexadecylene, 1-octadecylene, 1-icosa alkene, 1-docosene, 1-bis-tetradecenes, 1-cerotene, 1-bis-octadecylenes and 1-30 alkene, and these alpha-olefins can be used alone or as two kinds or use more than the mixture of two kinds;
The ester of-unsaturated carboxylic acid, (methyl) alkyl acrylate for example, this alkyl can have maximum 24 carbon atoms, and the example of alkyl acrylate or alkyl methacrylate is methyl methacrylate, ethyl propenoate, n-butyl acrylate, isobutyl acrylate and 2-EHA especially;
The vinyl acetate of-saturated carboxylic acid, for example vinyl-acetic ester or propionate;
-diene, for example Isosorbide-5-Nitrae-hexadiene.
Polyethylene can comprise multiple aforementioned comonomer.
Advantageously, this polymkeric substance can be the mixture of multiple polymers, and it comprises at least 50%, preferably more than 75% (by mol) ethene; Its density can be 0.86 to 0.98 gram/cc.MFI (at 190 ℃, the viscosity index under 2.16kg) is advantageously 5 to 100 grams/10 minutes.
As poly example, can mention:
-Low Density Polyethylene (LPDE);
-high density polyethylene(HDPE) (HPDE);
-LLDPE (LLPDE);
-very low density polyethylene (VLDPE);
-the polyethylene that obtains by metallocene catalyst;
-EPR (ethylene-propylene-rubber) elastomerics;
-EPDM (ethylene-propylene-diene) elastomerics;
The mixture of-polyethylene and EPR or EPDM; With
-ethene-(methyl) alkyl acrylate copolymer, it can contain maximum 60%, preferably (methyl) acrylate of 2% to 40 % by weight.
Grafting is known operation itself.
For the multipolymer of ethene and X, that is, the multipolymer of grafting X not wherein, it is ethene, X and the multipolymer of other monomer optionally, described other monomer can be selected from cited to the ethylene copolymer for grafting comonomer above.
Advantageously use ethene-maleic anhydride and ethene-(methyl) alkyl acrylate-copolymer-maleic anhydride.These multipolymers advantageously comprise 0.2 % by weight to 10 % by weight maleic anhydride and 0% to 40%, preferably 5 % by weight to 40 % by weight (methyl) alkyl acrylates.Their MFI is 5 to 100 (190 ℃-2.16kg).This (methyl) alkyl acrylate has above been described.Fusing point is 60 to 100 ℃.
Advantageously, each chain on average has at least 1.3 moles of X to be connected on polyolefin backbone, and preferably 1.3 to 10, more preferably 1.3 to 7.Those skilled in the art can easily analyze by IRTF these mole numbers of measuring X.
For having aminoterminal polymeric amide, polymeric amide is understood to following condensation product:
-one or more amino acid, as hexosamine, 7-aminoheptylic acid, the amino undecanoic acid of 11-and 12 amino dodecanoic acid;
-one or more lactan, as hexanolactam, oenantholactam and laurolactam;
-diamines, as hexanediamine, dodecane diamines, m-xylene diamine, two-p-aminocyclohexyl methane and trimethylammonium hexanediamine, with diacid, as one or more salt or the mixture of m-phthalic acid, terephthalic acid, hexanodioic acid, nonane diacid, suberic acid, sebacic acid and dodecanedioic acid;
-or the mixture of various of monomer, it produces copolyamide.
Can use the mixture of polymeric amide or copolyamide.Advantageously use PA 6, PA 11, PA 12, there is the copolyamide (PA 6/11) of 6 unit and 11 unit, the copolyamide (PA6/12) with 6 unit and 12 unit and the copolyamide based on hexanolactam, hexanediamine and hexanodioic acid (PA 6/6-6).The advantage of copolyamide is, can select thus the fusing point of grafting.
The homopolymer that this grafting advantageously forms for the residue by hexanolactam, the amino undecanoic acid of 11-or laurolactam, or the copolyamide being formed by the residue of at least two kinds being selected from aforementioned three kinds of monomers.
The polymerization degree can change in vast scale; According to its value, this product is polymeric amide or polyamide oligomer as well as.Hereinafter, to grafting, can use these two kinds of expression indistinction.
For making polymeric amide have monoamine end-blocking, it is enough using the chain terminator of following formula:
Wherein:
-R 1hydrogen or the straight or branched alkyl that contains maximum 22 carbon atoms;
-R 2to there is the straight or branched alkyl of maximum 22 carbon atoms or alkenyl, saturated or unsaturated cycloaliphatic group, aromatic group or aforesaid combination.
This terminator can be, for example, and lauryl amine, stearylamine or oleyl amine.
Advantageously, described grafting (having aminoterminal polymeric amide) has the weight-average molar mass that is less than 5000 grams/mol, and it is for example 1000 to 5000 grams/mol, preferably 2000 to 4000 grams/mol.
Most preferably, described grafting (having aminoterminal polymeric amide) has the mumber average molar mass that is less than or equal to 5000 grams/mol, and it is for example 1000 to 5000 grams/mol, preferably 2000 to 4000 grams/mol.
Be preferred for the amino acid of synthetic monoamine oligopolymer of the present invention or lactam monomers select oneself lactan, the amino undecanoic acid of 11-or laurolactam.Preferred simple function polymerization terminator is lauryl amine, stearylamine and oleyl amine.Above-mentioned polycondensation, under vacuum or in inert atmosphere, is carried out according to known method at the temperature of common 200 to 300 ℃ for example in stirred reaction mixture.The mean chain length of this oligopolymer by can polycondensation monomer or lactan and this simple function polymerization terminator between initial molar ratio determine.In order to calculate mean chain length, each oligomer chain has a chain terminator molecule conventionally.
Amine official by this oligopolymer can add to monoamine polyamide oligomer as well as on the polyolefin backbone that comprises X with reacting of X.Advantageously, X, with acid anhydrides or sour official energy, produces acid amides or imide bond thus.
Preferably in molten state, carry out amine end oligopolymer to add on the polyolefin backbone that comprises X.Thus, in forcing machine, can be at the temperature of common 230 to 250 ℃ this oligopolymer of mix and skeleton.The mean residence time of melting material in this forcing machine can be 1 to 3 minute.By the selective extraction polyamide oligomer as well as that dissociates, that is, unreacted forms those oligopolymer of the final graft copolymer with polyamide-block, evaluates and tests the yield of this addition.
In patent US 3,976,720, US 3,963,799, US 5,342,886 and FR 2,291,225, described and thisly there is the preparation of aminoterminal polymeric amide and they are added on the polyolefin backbone that comprises X.
The graft copolymer with polyamide-block of the present invention is with the nano-structured feature that is organized as.In these multipolymers, by the polyamide film of thickness 10 to 50 nanometers, or when the fusing point of polyolefin backbone is during than low at least 40 ℃ of the fusing point of polymeric amide grafting, by the midpoint being respectively the interval between polyolefin backbone fusing point and polymeric amide grafting fusing point, by the Young's modulus that is greater than 0.5MPa that the thermomechanical analysis under 1Hz frequency records on Rheometrics type dynamic rheometer, define nano-structured tissue.
Can advantageously by those skilled in the art, use known transmission electron microscopy and standard picture process software to measure the thickness of polyamide film.
According to a specific embodiments, this graft copolymer with polyamide-block can present the form of its precursor that the mixture by the aminoterminal polymeric amide grafting of polyolefin backbone+have forms.
In this case, by by polyolefin backbone with have aminoterminal grafting and mix to come original position to manufacture graft copolymer (C), final mixture should produce TPV.
The object of the invention is also thermoplastic compounds crosslinked or sulfuration, it is characterized in that it is formed by (A), (B) and mixture (C) as defined above, wherein the elastomerics of composition (B) and composition (A) and (C) be crosslinked between mixing period or vulcanize.
The invention still further relates to and prepare the method for composition as defined above, it is characterized in that being enough to mix composition (B) and composition (A) and preparation (C) at the elastomeric temperature of crosslinked or sulfuration composition (B) and in time span.These class methods are known as " dynamic vulcanization or crosslinking ".This mix can be in conventional apparatus, and as carried out at the temperature of about 150 ℃ to 240 ℃ the time of about 3 to 15 minutes in Banbury mixer, Brabender mixing machine, Rheocord mixing machine or forcing machine, temperature is higher, and this time is shorter.
The present invention finally relates to end article, its at least one composition is obtained by composition as defined above or obtains by method as defined above, or pass through the technology of usually conduct plastics by the mixture of crosslinked or sulfuration thermoplastic composition and the composition (C) of (A)+(B), such as but not limited to, extrude or co-extrusion, extrusion coated, injection molding, compression moulding, roll, be deposited on cable ( ), the powder deposition after grinding, comprise by electrostatic spray method, fluidized-bed pickling process, laser formation method, rotor moulding method or " slush moulding method " acquisition, after described, a method is well known by persons skilled in the art and refers to that by powder the unrestricted flow in mold heat carries out the method for molding, is particularly useful for manufacturing " shell " of dashboard, door-plate or supervisory control desk.
Therefore this based article is single material or many material products, and can comprise the plate of tackiness agent for example or tackiness agent, coating, film, single or multiple lift form or sealing agent that flexible tubing, building and automotive industry are used, protection bellows (soufflet de protection) that automotive industry is used and the injection molded article of single material or many material forms.
The present invention finally relate to there is polyamide-block graft copolymer as crosslinked or the surface properties of thermoplastic compounds of sulfuration or the purposes of the improving agent of thermodynamic property, described multipolymer is formed and is had nano-structured tissue by polyolefin backbone and on average at least 1.3 the polymeric amide grafting on described skeleton, and wherein said grafting can be connected on skeleton with the residue with the unsaturated monomer (X) of the functional group of aminoterminal polyamide reaction by having; And the described residue of described unsaturated monomer (X) is fixed to skeleton by grafting or copolymerization from its pair of key, described improving agent is introduced directly into and stands in dynamic vulcanization or crosslinked mixture, or mixes with described sulfuration or crosslinked thermoplastic compounds when sulfuration or crosslinked thermoplastic compounds are used.
Composition of the present invention can be especially, but be not limited to, in aforementioned articles of the present invention with other polymeric material, as polymeric amide or polyolefine, or with metal, glass combination.
These goods can be used in various uses; provide the example below, but never limit the scope of the invention: the protection bellows that the sealing agent that fuel or cooling fluid transfer tube, cable, cable transmission sheath, tackiness agent, thermal-protective coating or coating, building and automotive industry are used and automotive industry are used.
The present invention of the following example illustration, but do not limit its scope.In these embodiments, unless otherwise specified, otherwise umber and percentages.
embodiment 1 (contrast):
Object of reference is to be the thermoplastic elastomer that the polypropylene A of 2 grams/10 minutes (at 230 ℃ under 2.16kg) and the system of 65% use based on resol are cross-linked and the preparation EPDM B that comprises 150pcr aliphatic oil forms by 35%MFI.
the composition of B
EPDM 100pcr
The polyphenol linking agent 12pcr with 4 to 5 the polymerization degree
Zinc oxide promotor 12pcr
Aliphatic plasticizer 150pcr
Kaolin 40pcr
Titanium oxide pigments 10pcr
This thermoplastic elastomer has 65 Xiao A hardness and 35% the compression set recording at 80 ℃.
It is standing 4.9 * 10 4pa (0.5kg/cm 2) creep resistance on the injection molding bar of stress at 180 ℃ can ignore, because sample ruptures rapidly.
The Young's modulus of its recording with 1Hz frequency with Rheometrics type dynamic rheometer at 180 ℃ is less than 0.1MPa.
embodiment 2 (contrast):
With 80rpm rotation 8 minutes and be adjusted on the Brabender mixing machine of 180 ℃, manufacture consists of the mixture of 75% embodiment 1 (35 % by weight MFI are that the polypropylene A+65 % by weight of 2 grams/10 minutes (at 230 ℃ under 2.16kg) comprises cross-linking system based on resol and the preparation EPDM elastomerics B of 150pcr aliphatic oil) and has added the alloy that 25 % by weight have the graft copolymer C of polyamide-block, this graft copolymer C is not synthetic by the method described in WO 02/28959: the polyamide 6 that this graft copolymer with polyamide-block is 40000 grams/mol by 80% maleation that contains 1 % by weight grafted maleic anhydride (mal é is é) polypropylene and 20% weight average molecular mass forms.
With respect to embodiment 1, the binding property of improving with polymeric amide of can take is object, has the interpolation of the graft copolymer of polyamide-block.
Gained thermoplastic elastomer have 75 Xiao A hardness and 40% at the compression set of 80 ℃.
It is standing 4.9 * 10 4pa (0.5kg/cm 2) creep resistance on the injection molding bar of stress at 180 ℃ can ignore, because sample ruptures rapidly.
The Young's modulus of its recording with 1Hz frequency with Rheometrics type dynamic rheometer at 180 ℃ is less than 0.1MPa.
embodiment 3, according to the present invention:
With 80rpm rotation 8 minutes and be adjusted on the Brabender mixing machine of 180 ℃, we manufacture by the mixture of 75% embodiment 1 (35 % by weight MFI are that the polypropylene A+65 % by weight of 2 grams/10 minutes (at 230 ℃ under 2.16kg) comprises cross-linking system based on resol and the preparation EPDM elastomerics B of 150pcr aliphatic oil) and form and added the alloy that 25 % by weight have the graft copolymer C of polyamide-block, by the method described in WO 02/28959, polyamide 6 grafting synthetic and that be 3000 grams/mol by 80% ethylene/ethyl acrylate/maleic anhydride terpolymer (weight content is 80/17/3) and 20% weight average molecular mass forms this graft copolymer C.
Gained thermoplastic elastomer have 70 Xiao A hardness and 40% at the compression set of 80 ℃.
It is standing 4.9 * 10 4pa (0.5kg/cm 2) creep on the injection molding bar of stress at 180 ℃ was 50% after 15 minutes.
The Young's modulus of this composition recording with 1Hz frequency with Rheometrics type dynamic rheometer is greater than 0.5MPa.
Therefore, it is found that, added according to the product of embodiment 3, showing thus beguine according to much better the passing through in the creep test of 180 ℃ or the thermomechanical property that characterizes the Young's modulus measurement of 180 ℃ of the product of embodiment 1 and 2 by the synthetic PA graft copolymer of the method described in WO 02/28959.
Also find, the composition according to the present invention of embodiment 3 is less than the composition of embodiment 2 with respect to the changes in hardness of reference group compound with respect to the changes in hardness of reference group compound (according to embodiment 1).

Claims (25)

1. mixture, its every 100 weight parts (A)+(B) comprise:
(A) the structurized olefinic thermoplastic polymer of at least one non-nano of 15 to 75 weight parts;
(B) elastomeric preparation that at least one of 85 to 25 weight parts has unsaturated double-bond and can react with crosslinked or vulcanizing agent, described preparation comprises described one or more elastomeric being cross-linked or vulcanization system, at least one softening agent and conventional additive in elastomer formulation;
(C) with respect to (A)+(B), at least one of 10 to 90 weight parts has the graft copolymer of polyamide-block, described multipolymer is formed and is had nano-structured tissue by polyolefin backbone and on average at least 1.3 the polymeric amide grafting on described skeleton, and wherein said grafting can be connected on skeleton with the residue with the unsaturated monomer (X) of the functional group of aminoterminal polyamide reaction by having; And the described residue of described unsaturated monomer (X) is fixed to skeleton by grafting or copolymerization from its pair of key, wherein " polyolefin backbone " refers to homopolymer or the multipolymer of alpha-olefin or diolefine;
(A) in this mixture and (B) optionally by dynamic vulcanization or crosslinking combined to produce sulfuration or crosslinked thermoplastic compounds.
2. mixture as claimed in claim 1, is characterized in that composition (C) forms at most 50 % by weight of mixture (A)+(C).
3. the mixture as described in claim 1 to 2 any one, is characterized in that the described structurized olefinic thermoplastic polymer of at least one non-nano is selected from Alathon, alfon, ethene and C 3-C 8the multipolymer of alpha-olefin, with (methyl) vinylformic acid and C 1-C 8the multipolymer of the ester of alcohol and with the multipolymer of vinyl-acetic ester.
4. the mixture as described in claim 1 to 2 any one, is characterized in that the unsaturated elastic body of composition (B) is selected from:
The terpolymer EPDM of-ethene, propylene and diene;
-the natural or synthetic elastomerics based on divinyl;
-elastomerics based on isoprene;
-acrylic elastomer.
5. the mixture as described in claim 1 to 2 any one, it is characterized in that diene elastomer, crosslinked or vulcanization system is selected from the vulcanizing agent based on sulphur, superoxide, resol, azo-based, maleimide amino, quinonoid compound and urethane compounds; For having the acrylic elastomer of acidic group, it is selected from based on polyfunctional amine, or the reagent based on vulcabond; Or for having the acrylic elastomer of epoxide group, it is selected from the reagent based on ammonium salt, glyoxal ethyline or polyfunctional acid's molecule.
6. the mixture as described in claim 1 to 2 any one, it is characterized in that this crosslinked or vulcanization system constituent (B) 1 to 20pcr.
7. the mixture as described in claim 1 to 2 any one, it is characterized in that softening agent constituent (B) 5 to 200pcr, and especially, for thering is the elastomerics of unsaturated double-bond, select the oil of the mixture formation of free aliphatic series, cycloalkanes or aromatic hydrocarbon, for acrylic elastomer, be selected from the polar oil based on phthalic ester.
8. the mixture as described in claim 1 to 2 any one, is characterized in that typical additives is selected from powdery mineral filler, pigment, coupling agent, anti degradant, processing additives, wax, and especially constituent (B) 10 to 150pcr.
9. the mixture as described in claim 1 to 2 any one, is characterized in that X is unsaturated carboxylic acid anhydrides.
10. mixture as claimed in claim 9, is characterized in that the polyolefin backbone that comprises X is selected from ethene-maleic anhydride and ethene-(methyl) alkyl acrylate-copolymer-maleic anhydride.
11. mixtures as described in claim 1 to 2 any one, is characterized in that having average 1.3 to 10 moles of X to be connected on the polyolefin backbone of composition (A).
12. mixtures as claimed in claim 11, is characterized in that having average 1.3 to 7 moles of X to be connected on the polyolefin backbone of composition (A).
13. mixtures as described in claim 1 to 2 any one, it is characterized in that this grafting is the homopolymer that the residue by hexanolactam, 11-amino-undecanoic acid or laurolactam forms, or the copolyamide being formed by the residue of at least two kinds being selected from aforementioned three kinds of monomers.
14. mixtures as described in claim 1 to 2 any one, is characterized in that this grafting has the weight-average molar mass that is less than 5000 grams/mol.
15. mixtures as described in claim 1 to 2 any one, is characterized in that the polyolefin backbone of the graftomer of composition (C) is selected from Alathon, alfon, ethene and C 3-C 8alpha-olefin, with (methyl) vinylformic acid and C 1-C 8the ester of alcohol and with the multipolymer of vinyl-acetic ester.
16. mixtures as described in claim 1 to 2 any one, the graft copolymer described in it is characterized in that with polyamide-block shows nano-structured tissue, wherein the thickness of polyamide film is 10 to 50 nanometers, or when the fusing point of polyolefin backbone is during than low at least 40 ℃ of the fusing point of polymeric amide grafting, the Young's modulus recording by the thermomechanical analysis when the midpoint that is respectively interval between polyolefin backbone fusing point and polymeric amide grafting fusing point is used Rheometrics type dynamic rheometer in 1Hz frequency is greater than 0.5MPa.
17. mixtures as described in claim 1 to 2 any one, its precursor forms that the graft copolymer described in it is characterized in that with polyamide-block forms with the mixture by the aminoterminal polymeric amide grafting of polyolefin backbone+have exists.
18. mixtures as described in claim 1 to 2 any one, is characterized in that this grafting has the mumber average molar mass that is less than 5000 grams/mol.
The thermoplastic compounds of 19. crosslinked or sulfurations, is characterized in that it is formed by the mixture as described in claim 1 to 18 any one, wherein the elastomerics of composition (B) and composition (A) and (C) be crosslinked between mixing period or vulcanize.
The method of 20. preparation composition as claimed in claim 19, is characterized in that being enough to mix composition (B) and composition (A) and preparation (C) at the elastomeric temperature of crosslinked or sulfuration composition (B) and in time span.
21. methods as claimed in claim 20, is characterized in that at the temperature of 150 ℃ to 240 ℃, during the time span of 3 to 15 minutes, carry out mix.
22. end articles, its at least one integral part is obtained by composition as claimed in claim 19 or obtains by the method as described in claim 20 or 21.
23. end articles, its at least one integral part is obtained by the mixture as described in claim 1-18, wherein this at least one integral part by the mixture of crosslinked or sulfuration thermoplastic composition and the composition (C) of (A)+(B) by extrude or coextrusion, extrusion coated, injection molding, compression moulding, roll, be deposited on cable, powder deposition technology after grinding obtains, and is particularly useful for manufacturing " shell " of dashboard, door-plate or supervisory control desk.
24. goods as described in claim 22 or 23, is characterized in that sealing agent that plate that it comprises tackiness agent, coating, film, single or multiple lift or flexible tubing, building and automotive industry use, protection bellows that automotive industry is used and the injection molded article of single material or many materials.
25. graft copolymers with polyamide-block are as crosslinked or the surface properties of thermoplastic compounds of sulfuration or the purposes of the improving agent of thermodynamic property, described multipolymer is formed and is had nano-structured tissue by polyolefin backbone and on average at least 1.3 the polymeric amide grafting on described skeleton, and wherein said grafting can be connected on skeleton with the residue with the unsaturated monomer (X) of the functional group of aminoterminal polyamide reaction by having; And the described residue of described unsaturated monomer (X) is fixed to skeleton by grafting or copolymerization from its pair of key, described improving agent is directly introduced and is stood in dynamic vulcanization or crosslinked mixture, or mixes with described sulfuration or crosslinked thermoplastic compounds when sulfuration or crosslinked thermoplastic compounds are used.
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US20100270820A1 (en) 2010-10-28
FR2918380A1 (en) 2009-01-09

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